Adhesive products of polyisocyanates and polyisothiocyanates



United States Patent 0 3,226,354 ADHESIVE PRODUCTS 0F POLYISOCYANATESAND PElLYlSOTl-HOCYANATES Herbert L. Heiss, Cider Run, New Martinsville,W. Va.,

assiguor to Monsanto Company, St. Louis, Mo., a corporation of DelawareNo Drawing. Continuation of application Ser. No. 373,035, Aug. 7, 1953.This application Sept. 28, 1959, Ser. No. 842,593

21 Claims. (Cl. 26031.2)

This application is a continuation of application Serial No. 373,035,filed August 7, 1953, and now abandoned, which was acontinuation-in-part of application Serial No. 300,968, filed July 25,1952, and now abandoned.

This invention relates to organic chemical compositions and particularlyto polymeric compounds.

This invention has as an object the provision of an improved method ofpreparing polyhydric materials. A further object of the invention is toprovide an improved method of producing polymeric materials from organicpolyisocyanates and/or polyisothiocyanates and organic materialscontaining a plurality of active hydrogen atoms, whereby the rate atwhich these materials react together is greatly increased. Anotherobject is the preparation of polymeric materials which can be utilizedin the manufacture of films, fibers and plastics. A still further objectof the invention is to provide polymeric materials having improvedcuring and bonding properties over those obtainable by methods of theprior art. Other objects and advantages will appear hereinafter as thedescription of the invention proceeds.

The foregoing objects are achieved by reacting, in the presence of acatalyst of the type hereinafter specified, an organic compound having aplurality of but preferably two separate and distinct reactive groups ofthe formula -NCX wherein X is selected from the group consisting ofoxygen and sulfur, with an organic sub stance having a plurality ofgroups, each of which con tains reactive hydrogen. The reactive hydrogenis that detected and determined by the Zerewitinofi method. When thereactants are bifunctional, i.e., when one reactant contains two groupsof the formula -NCX and the other reactant contains two groups withreactive hydrogen, the products are usually linear polymers. When one ofthe reactants is already polymeric, the product is a modified polymer ofhigh molecular weight.

In producing polymeric materials by the method of the instant invention,there is employed a catalyst which is selected from the group consistingof compounds capable of yielding in aqueous solution ionizablehydroxylor substituted hydroxyl groups and precursors of thesecompounds. The expression substituted hydroxyl groups signifies radicalsof the formula -OX, in which X is a member selected from the groupconsisting of aliphatic, stituted hydrocarbon radicals which may or maynot be interrupted by non-reactive hetero atoms such as sulfur andoxygen, etc. For example, these hydrocarbon radicals may be substitutedby alkyl, alkoxy, halogen and/or nitro groups. Illustrative examples ofsuitable catalysts are the oxides or hydroxides of alkali and alkalineearth metals such as potassium, sodium, calcium, barium and strontium;the oxides of zinc and lead; the alkali metal salts and particularly thesodium and potassium salts of substituted phenols such as orthophenylphenol, 2,4,5- trichlorophenol and 2,3,4,6-tetrachlorophenol; andquaternary ammonium bases such as benzyl trimethylammonium hydroxide,tetramethylammonium hydroxide, tetramethylphenylammonium hydroxide,tetraethylammonium hydroxide, etc. These catalysts are used alone or incombination with tertiary organic amines such cycloaliphatic, aryl,alkaryl, aralkyl and subas N-methylmorpholine, N-ethylmorpholine,triethylamine, tripropylamine, tributylamine, triamylamine, pyridine andquinoline, etc. The sodium salts of the substituted phenols are mostpreferred.

The present invention is illustrated by the following examples, whereinparts given are by weight. There are, of course, many other forms of theinvention other than these specific embodiments.

Example I 13.8 parts of a polyethylene glycol having an averagemolecular weight of about 400 was mixed with about 12 parts ofm-tolylene diisocyanate and the ensuing reaction allowed to proceedwithout the addition of heat until the reactants yielded a solidifiedresinous polymer.

The foregoing procedure was repeated except that the reaction wascarried out in the presence of varying amounts ofbenzyltrimethylammonium hydroxide, the purpose being to determine theeffect of this catalyst on the reaction rate between the glycol and thediisocyanate.

The quantities of benzyltrimethylammonium hydroxide and the maximumreaction temperatures and reaction times employed are set forth below:

These experimental data clearly demonstrate that the rate of reactionbetween the polyethylene glycol and d isocyanate is greatly increased bymeans of benzyltrimethylammonium hydroxide and that the rate of increaseincreases with the concentration of the catalyst.

Example 2 Approximately 12 parts of m-tolylene diisocyanate and about13.8 parts of a polyethylene glycol having an average molecular weightof about 400 were reacted together at room temperature in the presenceof a sufiiclent amount of ethyl acetate to yield a 50 percent solutionof the corresponding adduct. Samples of this solution were converted toa more highly polymerized state by continuing the reaction in thepresence of moisture and in the presence and absence of catalysts, thepurpose being to determine the effect of the catalyst on the curingrate. The catalyst used, the amount of catalyst and the results obtainedare given in the following table:

Curing Time at Adduct Catalyst Room Tem- Solution No. perature, MinutesNone 2330 2.5% by Wt. of N-methylmorpho1ine 300 0.08%Benzyltrimethylammonium Hy- 120 droxide. 4 0.08%Benzyltrirnethylammonium Hy- 30 ilroxide and 2.5% N-methylmorphome. 50.2% Benzyltrimethylammonium Hy- 120 droxide. 6 0.2%Benzyltrirnethylammonium Hy- 3O {lroxide and 2.5% N-methyhuorpho- 1119.7 0.64% Benzyltrirnethylammonium I-Iy- 25 iiroxide and 2.5%N-methyhnorphome. 8 0.2% Benzyltrimethylammonium Hy- 10 droxide and 5%N-methyhnorpholine.

The experimental data given in this table clearly demonstrate thatN-methylmorpholine and benzyltrirnethylammonium hydroxide markedlyincrease the rate at which the reactants are converted to a resinoussolid polymer. They also show that the use of N-methylmorpholine incombination with benzyltrimethylammonium hydroxide products asynergistic effect in that the rate of reaction thus obtained is greaterthan the sum of the individual effects.

Example 3 Samples of the adduct solutions designated 1 and 8 in Example2 were used as adhesives in laminating /2" x A x 1% aluminum plates. Inproducing these products, the surfaces of an aluminum foil were coatedwith the adhesive and then the coated foil was inserted between thealuminum plates. The resulting assembly was heated while under slightpressure at a temperature of about 175 C. for minutes or until thepolymer fused. The product prepared in this manner were subjected to anincreasing load applied perpendicularly to the plane of lamination untilthe sheets separated. The load at which failure occurred is set forthbelow:

Adduct No. Load of Failure Lbs/Sq. In.

About 600. About 1,600.

Example 4 m-Tolylene diisocyanate and the condensate of about 6.6 molsof propylene oxide with 1 mol of glycerine were reacted together in aweight ratio of about 7.85 parts of the diisocyanate to about 7.15 partsof the condensate, the reaction taking place in the presence of asufficient amount of chlorinated biphenyl containing 42 percent chlorineto yield a 50 percent solution of adduct. On continuing the reaction byheating for 2% hours at 140 C,, a sample of this solution yielded atough, rubbery and resinous gel.

The procedure just described was followed except that 1 percent byweight of calcium oxide was added to a sample of the solution of adduct.On continuing the reaction by heating the sample at 140 C. for minutes,it was converted initially into a gel and finally into a porous resinousfoam.

This example demonstrates that the rate at which the glycol is convertedby the diisocyanate to a resinous polymer is greatly accelerated by theuse of calcium oxide.

Example 5 rn-Tolylene diisocyanate containing about 0.23 percent ofhydrolyzable chlorine was reacted with the condensate of about 3.1 molsof propylene oxide with 1 mol of glycerine in a weight ratio of 9.86parts of the isocyanate to about 5.14 parts of the condensate, thereaction taking place in the presence of sufficient amount ofchlorinated biphenyl containing 42 percent chlorine to yield a 50percent solution of the adduct. The reaction was continued by heatingthe solution at 150 C. for 3 hours and a gel was formed which, oncontinued heating for a total of 23 hours at the same temperature,produced a flexible, bubble-free resin.

The foregoing procedure was repeated except that about 1 percent byweight of lead oxide was added to a sample of the solution of adduct andthe reaction continued by heating at 140 C. for about 1%. to 1% hours.This resulted in the conversion of the solution into a gel and finallyinto a rubbery resinous foam.

This example demonstrates that the use of lead oxide greatly increasesthe rate at which the condensate is converted by the diisocyanate into asolid resinous product.

Example 6 About 23.4 parts of m-tolylene diisocyanate was added, withagitation, to a solution of about 26.7 parts of a polyethylene glycolhaving an average molecular weight of about 400 in about 50 parts ofanhydrous benzene. After the ensuing reaction subsided, about 2.5 partsof N-methylrnorpholine was added. A sample of this product was appliedas a film to the surface of glass and the reaction continued until thesolution was converted to a non-tacky stage.

The procedure just described was repeated except that about 0.01 percentby weight of KOH was added to the polyethylene glycol used in thereaction.

The periods of time required to convert the sample solutions to anon-tacky stage were as follows:

Conversion time, minutes Sample prepared without KOH catalyst 500 Sampleprepared with KOH catalyst About 20 Samples of the solutions ofintermediate reaction product prepared in the foregoing manner were usedto coat a 0.001 inch aluminum foil which in turn was employed as aninterlayer in forming laminated aluminum plates. The laminated plateswere prepared by assembling the interlayer between the plates and thensubjecting the assembly to a temperature of C. and a pressure of about50 lbs/sq. in. The laminated products thus prepared were subject to anincreasing load applied perpendicularly to the plane of lamination untilthe sheets separated. The load at which failure occurred is set forthbelow:

Load of failure, Laminated product: lbs/sq. in.

Prepared from adhesive made without This example demonstrates that theuse of KOH results F in the production of an adhesive having greatlyincreased bond strength over a similar adhesive produced in the absenceof KOH.

The invention is applicable to the reaction of compounds having aplurality of groups containing reactive hydrogen, as determined by theZerewitinoff method, with a compound having a plurality of separate anddistinct groups of the formula -NCX wherein X is a member selected fromthe group consisting of oxygen and sulfur. Compounds containing aplurality of NCX groups include diisocyanates, triisocyanates,diisothiocyanates and triisothiocyanates, etc., as well as com pounds ofthe mixed functions such as the isocyanateisothiocyanates.

The preferred compounds are those having two groups of the formula -NCXand of these the diisocyanates and diisothiocyanates in general are mostuseful in the practice of this invention and form a preferred subclassbecause of their ease of preparation, low cost, reactivity, etc.Additional examples of this preferred subclass are ethylenediisocyanate, t-rimethylene diisocyanate, tetramethylene diisocyanate,pentamethylene diisocyanate, etc.; and the correspondingdiisothiocyanates; alkylene diisocyanates and diisothiocyanates, such aspropylene-1,2-diisocyanate, butylene 1,2 diisocyanate, butylene1,3-diisocyanate, butylene2,3-diisocyanate, andbutylene-1,3-diisothiocyanate; alkylidene diisocyanates anddiisothiocyanates, such as ethylidine diisocyanate, butylidinediisocyanate and ethylidine diisothiocyanate; cycloalkylenediisocyanates and diisothiocyanates, such ascyclopentylene-1,3-diisocyanate, cyclohexylene-1,2-diisocyanate,cyclohexylene-1,3-diisocyanate, cyclohexylene-1,4-diisocyanate, andcyclohexylene-l,Z-diisothiocyanate; cycloalkylidene diisocyanates anddiisothiocyanates, such as cyclopentylidene diisocyanates,cyclohexylidene diisocyanate and cyclohexylidene diisothiocyanate;aromatic diisocyanates and diisothiocyanates, such as m-phenylenediisocyanate, p-phenylene diisocyanate, l-methyl-Z- i-phenylenediisocyanate, naphthyl isocyanate, 1-methyl-2,4-phenylene diisocyanate,naphthylene-l,4-diisocyanate, diphenylene-4,4-diisocyanate orp-phenylene diisothiocyanate; aliphatic-aromatic diisocyanates ordiisothiocyanates, such as sylylene-l,4-diisocyanate,xylylene-l,3--diisocyanate, 4,4-diphenylenemethane diisocyanate,4,4diplienylene-propane diisocyanate or xylylene-1,4-diisothiocyanate;and diisocyanates and diisothiocyanates containing hetero atoms, such asSCNCH O CH NCS,

In fact, any diisocyanate, diisothiocyanate, or mixedisocyanate-isothiocyanate of the general formula XCNRNCX in which X isoxygen or sulfur and R is a divalent organic radical, will react withthe reactive hydrogen compound to give polymers according to the presentinvention.

As examples of compounds containing more than two reactive groups of theformula NCX, there may be mentioned butane 1,2,2-triisothiocyanate,1,2,4-benzene triisothiocyanate, 4-,4,4*triphenylmethanetriisothiocyanate, 2,4,4-biphenyl triisothiocyanate, 1,4,7-naphthalenetriisothiocyanate, 2,4,7-naphthalene triisothiocyanate,4,4,4"-m-terphenyl triisothiocyanate, 4,4,4"oterphenyltriisothiocyanate, butane l,2,2triisocyanate, 1,2,4-benzenetriisocyanate, 4,4,4"-triphenylmethan-e triisocyanate, 2,4,4-biphenyltriisocyanate, 1,4,7-naphthalene triisocyanate, 2,4,7-naphthalenetriisocyanate, 4,4,4"-m-terphenyl triisocyanate and 4,4,4-o-terphenyltriisocyanate, etc.

The invention is generic to compounds having a plurality of groupscontaining reactive hydrogen. Typical groups containing reactivehydrogen are hydroxyl, carboxyl, primary amino, secondary amino, amido,and mercapto groups, etc.

Illustrative examples of suitable compounds within these various groupsare glycols such as ethylene glycol, propylene glycol, butyleneglycol-2,3, butylene glycol-1,3, 2 methylpentanediol 2,4,2-ethylhexanediol-1,3, hexamethylene glycol, styrene glycol,N-phenyl-diethanolamine, catechol, resorcinol, 2,2-bis(4-hydroxyphenyl)propane, p,p'-dihydroxybiphenyl, decamethylene glycol; polyglycols(ether glycols) such as polyethylene glycols, diethylene glycol,triethylene glycol, tetraethylene glycol, polyethylene glycols 200, 400and 600; polypropylene glycols, dipropylene glycol, tripropylene glycol,polypropylene glycols 400, 750, 1200 and 2000; carbowaxes 1000, lOOOW,1500; monoethers of trihydroxy compounds such as glyceri11eu-allylether, glyceryl-a-phenyl ether, glyceryl-a-isopropyl ether; hydroxyesters such as an ester prepared from 1 mol of dibasic acid and 2 molsof a glycol or polyglycol, a polyester prepared so that the molar ratioof glycol or polyglycol to the dibasic acid is between 2 and 1, an esterprepared from 1 mol of a dimer acid and 2 mols of a glycol orpolyglycol, an ester prepared from a hydroxy acid and a glycol orpolyglycol so that the molar ratio of the glycol or polyglycol to thehydroxy acid is between 0.5 and l and an ester prepared from 1 mol of atrihydroxy compound and 1 mol of a monobasic acid, such as themonoglyceride of eleostearic acid; trihydroxy compounds such asglycerine, triethanolamine, pyrogallol, phloroglucinol, etc., allryleneoxide condensates of glycerine, triethanolamine, pyrogallol,phloroglucinol, etc; monoethers of tetrahydroxy compounds; estersprepared from hydroxy acid and a trihydroxy compound so that the molarratio of the latter to the former is between 0.33 and 1, such asglycerine triricinoleate, esters prepared from 1 mol of a monobasic acidand 1 mol of a tetrahydroxy compound; tetrahydroxy compounds such aspentaerythritol, etc., alkylene oxide condensates of pentaerythritol,etc., esters prepared from 1 mol of a di'basic acid and 2 mols of atrihydroxy compound; pentahydroxy compounds, such as arabitol, xylitol,etc.; hexahydroxy compounds such as sorbitol, ducitol, mannitol;carboxyl compounds such as oxalic acid, malonic acid, pimelic acid,suberic acid, azelaic acid, decane-l,lO-dicarboxylic acid, itaconicacid, itamalic acid, cyclopentane-1,3-dicarboxylic acid,cyclohexane-1,2-dicarboxylic acid, cyclohexane-1,3-dicarboxylic acid,cyclohexane-l,4-dicarboxylic acid, diphenic acid, phthalic acid,isophthalic acid, terephthalic acid, naphthalene-1,2-dicarboxylic acid,naphthalene-1,3-dicarboxylic acid, naphthalenel,4-dicarboxylic acid,naphthalene-1,5-dicarboxylic acid, diphenylene-2,2-dicarboxylic acid,diphenylene-4,4- dicarboxylic acid, diphenylene-Z,4-dicarboxylic acid,xylylene-1,4-dicarboxylic acid, xylylene-l,3-dicarboxylic acid,xylylene-1,2-dicarboxylic acid, citric acid, tartaric acid,tricarballylic acid, polyacrylic acid, etc..; amines such as ethylenediamine, trimethylene diamine, tetramethylene diamine, hexarnethylenediamine, octamethylene diamine, d-ecamethylene diamine, dodecamethylenediamine, N,N'- dimethyl decamethylene diamine, N,N-dibenzylhexamethylene diamine, cyclohexylene-l,4-diamine, o-phenylene diamine,m-phenylene diamine, p-phenylene diamine, benzidine,naphthalene1,4-diamine, gamma,gamma'-diamino-dibutyl oxide,gamma,gamrna-diamino-dibutyl sulfide, diethylene triamine, triethylenetetramine, amides such as phthalamide, isophthalamide, terephthalamide,malonamide, succinamide, adipamide, etc. and the corresponding imides;mercaptans such as dimercapto-ethane, l,2,3-trimercaptopropane,l,2,3-trimercaptobutane, 1,5- dimercapto 3 me-rcaptomethylpentane,1,6-dimercaptohexane, 1,10-dimercaptodecane,l,6dimercapto-3-methylhexane, l,4-dirnercaptobenzene,dimercaptoxylylene, dimercaptoresorcinol and polyvinyl mercaptan; andpolyalkylene sulfides such as the thiokols.

Illustrative examples of polymeric materials having activehydrogen-containing groups which may be employed in the practice of thisinvention are hydroxylated organic materials such as cellulose; starch;dextrine; wood; cellulose derivatives containing hydroxyl, amino orother active hydrogen-containing groups including among others celluloseesters such as acetate, propionate, butyrate and nitrate; cellulosemixed esters; cellulose ethers such as methyl or ethyl cellulose;carboxylated cellulose; and regenerated cellulose; polyvinyl alcohol andpolyvinyl alcohol derivatives such as partially hydrolyzed polyvinylacetate or polyvinyl proprionate; polyvinyl acetal; polyvinyl ketals;and polyhydric alcohol-polybasic acid condensation products (alkydresins) with free hydroxyl or carboxyl groups.

Resins obtained by the condensation of formaldehyde with such materialsas phenols, amides (including ureas and sulfonamide), aldehydes,ketones, aromatic ethers, aromatic hydrocarbons, carbamates and aminesmay be used.

Nitrogen-containing polymeric materials are particularly useful. Forexample, polyester amides such as the condensation product ofethanolamine, adipic acid and ethylene glycol, or the condensationproduct of hexamethylene-diamine, adipic acid and ethylene glycol, or,in general, polymers formed by condensing a polyamine, a polybasic acidand polyhydric alcohol. Low or high molecular weight polyamides such aspolyhexamethylene adipamide, polydecamethylene adipamide, 6-aminocaproicacid polymer, and the like may be used. Protein and protein-likematerials such as gelatin, casein, zein and leather; gums such as copal,Congo, kauri, shellac and dammar; and polymerized or gelled drying oilsof the linoxyn type are also suitable.

Ether resins, for example, those prepared by reacting organicpolyhalides with polyhydric phenols as described in U.S. Patent2,060,175, and polymeric derivatives of acrylic, methacrylic or fumaricacid may also be used as polymeric organic materials containing activehydrogen atoms.

Active hydrogen-containing vulcanizable materials may be employedincluding aldehyde treated natural and synthetic rubbers, for example,those disclosed in US. Patents 1,915,808 and 1,640,363 and BritishPatent 486,878, rubber di-(hydroxy phenyl), and hydroxylated rubbers,e.g., the peracetylated rubbers and hydrolyzed peracetylated rubbersdescribed in US. Patent 1,988,448. The term rubber as used hereinincludes natural rubber, balata, gutta percha, modified rubber,neoprene, and the various butadiene and substituted butadiene polymersand interpolymers.

The organic compounds having a plurality of groups containing reactivehydrogen comprise compounds of the formula R (QH) wherein R is apolyvalent radical of valence x, x is an integer greater than 1, Q is abivalent group linking the reactive hydrogen through a polyvalentinorganic element such as oxygen, sulfur or nitrogen.

The reaction between the organic compound containing a plurality ofseparate and distinct groups having the formula NCX wherein X is amember of the class consisting of oxygen and sulfur with an organicsubstance having a plurality of groups containing reactive hydrogenatoms, may be carried out either in the presence or absence of solvents,diluents or plasticizers and at atmospheric, superatmospheric orsubatmospheric pressures. The reaction is preferably conducted in theabsence of oxygen or moisture, which may be achieved either by operatingin a partial vacuum or in the presence of an inert gas such as nitrogen.In most cases, the reaction proceeds at ordinary temperatures, but, ifdesired, higher temperatures may be employed. The above reaction doesnot require high temperatures and in general it is advantageous tooperate below 200 C.

The reaction of an organic compound of the general formula: R(NCX) withan organic polyhydroxy compound, particularly at organic dihydroxycompound, in the presence of a low boiling inert organic solvent, thatis, a solvent boiling below 200 C. at atmospheric pressure, results inthe production of a solution of reaction product, which cures at arelatively slow rate. This solution is activated by the addition ofabout 0.001 percent to about 5 percent by weight of a catalyst of theclass mentioned above. This activated solution finds use as an adhesiveor in protective coatings or in applications where it is desirable toapply a liquid to a surface and then allow it to cure or harden into asolid. For example, this solution may be used to adhesively bind variousbases together such as wood to wood, glass to glass, fiber board tofiber board, cloth to cloth, paper to paper, regenerated cellulose toregenerated cellulose, cellulose esters to cellulose esters, celluloseethers to cellulose ethers, gelatin to gelatin, mica to mica, steel tosteel, steel to aluminum, steel to cellulose acetate, steel to acrylicplastics, steel to vinyl plastics, steel to Wood and variouscombinations of these and other bases.

In the production of laminated products, the activated solution isapplied to one or both of the laminae, after which the laminae areassembled and the solution allowed to cure at room temperature whilebeing subjected to pressure. If desired, the curing may be acceleratedby subjecting the assembly to heat and pressure until the polymerizationof the above organic compound has been carried substantially tocompletion.

The adhesives prepared in the presence of catalysts in accordance withthis invention have novel and completely unexpected properties in thatthey are characterized by possessing a greatly accelerated curing rateand markedly improved bond strengths over similar adhesives prepared inthe absence of a catalyst.

In the production of adhesives in accordance with this invention, thereactants are employed in the proportions providing a ratio of -NCXgroups to active hydrogen atoms which falls substantially in the rangeof about 1:1 to about 11:1. More specifically, the reactants areemployed in the proportions providing a ratio of NCX groups to activehydrogen atoms which falls in the range of about 1.3:1 or 1.5:1 to about1221, and preferably in the range of about 2:1 to about It: 1.

As indicated earlier herein, an inert organic solvent boiling at atemperature below 200 C. and preferably below C, at atmospehric pressureis employed in carrying out the reaction. Illustrative examples ofsolvents suitable for use in this reaction are benzene, toluene, xylene,carbon tetrachloride, acetone, methyl ethyl ketone, ethyl acetate andamyl acetate. However, it is to be understood that the invention is notrestricted to these materials as other equivalent inert organic solventsmay be employed.

Polymers containing mixed organic radicals may be prepared by reacting acompound of the formula XCNR NCX with a compound of the formula H-Q- R-QH wherein R and R are different organic radicals. Moreover,interpolymers may be prepared by reacting two or more differentcompounds of the formula HQR QH with a single compound of the formulaXCNRNCX or vice versa.

The proportions of reactants used in the practice of the instantinvention may fluctuate widely since the invention resides primarily inthe use of the catalysts hereinbefore mentioned to substantiallyincrease the rate of reaction. In general, the reactants are employed ina molar ratio of the organic compound containing -NCX groups to theactive hydrogen-containing organic compound, which falls substantiallyin the range of about 1:1 to about 3:1 or vice versa, and within thisrange a molar ratio of the former to the latter of about 2:1 ispreferred. However, it is to be understood that the invention is notrestricted to these molar ratio ranges.

The catalysts used in the practice of the instant invention are employedin an amount varying from about 0.001 percent to about 5 percent byweight or, more specifically, within the range of about .01 percent toabout 3 percent by weight and within these limits about .05 percent toabout 1 percent is perferred. The percentage by weight is based upon theweight of the total reactants.

The products of the instant invention find use in the production offilms, fibers, textile finishing agents for improving the waterrepellency of treated fabrics, bristles and coating or moldingcompositions, bubble-free resins, resinous foams, potting resins,protective coatings, paints, varnishes, lacquers, laminated products,vibration, suppressors, radomes, abrasive articles, sound insulators,heat insulators, electrical insulators, condensers, coated electricalconductors, coil forms, stand'off insulators, insulating rods andbushings, coil mounting strips, insulating beads for coaxial cables,safety glass, plastic articles, packaging materials, adhesives, andnumerous other commercially attractive products.

The term chalcogen is a group name for the elements oxygen, sulfur,selenium and tellurium and of these, the first two have an atomic weightless than 33.

As many apparently widely different embodiments of this invention may bemade without departing from the spirit and scope thereof, it is to beunderstood that this invention is not limited to the specificembodiments thereof except as defined in the appended claims.

What is claimed is:

1. As a new composition of matter, an adhesive composition of greatlyaccelerated curing rate comprising a solution in an organic solventboiling below about 200 C. at atmospheric pressure of an organicmaterial obtained by reacting a compound of the general formula: R(NCX)wherein R is an organic radical free from functional groups other thanNCX groups, X is selected from the group consisting of oxygen andsulfur, and n is an integer having a value of at least 2, with anorganic compound having as the only groups reactive with an -NCX groupat least two groups selected from the group consisting of hydroxyl,carboxyl, primary amino, secondary amino and mercapto groups, saidsolution containing from about 0.001 percent to about percent by weightof a catalyst selected from the group consisting of the oxides andhydroxides of alkali and alkaline earth metals; the oxides of zinc andlead; the alkali metal salts of substituted phenols; and the uncomplexedquaternary ammonium compounds.

2. As a new composition of matter, an adhesive composition of greatlyaccelerated curing rate comprising a solution in an organic boilingbelow about 150 C. at atmospheric pressure of an organic materialobtained by reacting a compound of the general formula: R(NCO) wherein Ris an organic radical tree from functional groups other than NCO groups,and n is an integer having a value of at least 2, with an organiccornpound having as the only groups reactive with an -NCO group at leasttwo groups selected from the group consisting of hydroxyl, carboxyl,primary amino, secondary amino and mercapto groups, said solutioncontaining from about 0.001 percent to about 5 percent by weight of acatalyst selected from the group consisting of the oxides and hydroxidesof alkali and alkaline earth metals; the oxides of zinc and lead; thealkali metal salts of substituted phenols; and the uncomplexedquaternary ammonium compounds.

3. As a new product, a plurality of laminae bonded together by the curedadhesive defined in claim 1.

4. The method of making nonporous polyurethanes which comprises reactingan organic diisocyanate with a polyoxyalkylene glycol in the presence ofan organic solvent boiling below 200 C. at atmospheric pressure and fromabout 0.001 percent to about 5 percent by weight of a catalyst selectedfrom the group consisting of the oxides and hydroxides of alkali andalkaline earth metals; the oxides of zinc and lead; the alkali metalsalts of substituted phenols; and the uncomplexed quaternary ammoniumcompounds.

5. The method of making nonporous polyurethanes which comprises reactingan organic diisocyanate with a polyethylene glycol in the presence of aninert organic solvent boiling below 200 C. at atmospheric pressure andfrom about 0.01 percent to 3 percent by weight of a catalyst comprisingbenzyltrimethylammonium hydroxide.

6. The method of making nonporous polyurethanes which comprises reactingan organic diisocyanate with a propylene oxide-glycerine condensate inthe presence of an inert organic solvent boiling below 200 C. atatmospheric pressure and from about 0.01 percent to about 3 percent byweight of a catalyst selected from the group consisting of the oxidesand hydroxides of alkali and alkaline earth metals; the oxides of zincand lead; the alkali metal salts of substituted phenols; and theuncomplexed quaternary ammonium compounds.

7. A a new composition of matter, an adhesive composition of greatlyaccelerated curing rate comprising a solution in an inert organicsolvent boiling below 200 C. at atmospheic pressure of an organicmaterial obtained by reacting an organic diisocyanate with apolyoxyalkylene glycol, said solution containing about 0.001 percent toabout 5 percent by weight of a catalyst selected from the groupconsisting of the oxides and hydroxides of alkali and alkaline earthmetals; the oxides of zinc and lead; the alkali metal salts ofsubstituted phenols; and the uncomplexed quaternary ammonium compounds.

8. In a method for making nonporous polyurethane plastics by a processwhich comprises reacting an organic compound having at least two groupsselected from the group consisting of hydroxyl, carboxyl, primary amino,secondary amino and mercapto groups, said groups being the only groupsreactive with an NCX group, with an organic compound having as its solereactive groups a plurality of separate and distinct groups having theformula -NCX wherein X is selected from the group consisting of oxygenand sulfur, the improved method of effecting the said reactioncomprising carrying out the said reaction in the presence of from about0.001 percent to about 5 percent by weight of a catalyst selected fromthe group consisting of the oxides and hydroxides of alkali and alkalineearth metals; the oxides of zinc and lead; the alkali metal salts ofsubstituted phenols; and uncomplexed quaternary ammonium compounds.

9. In a method for making nonporous polyurethane plastics by a processwhich comprises reacting an organic compound having at least twohydroxyl groups as its only reactive groups with an NCX group, with anorganic compound having as its sole reactive groups a plurality ofseparate and distinct groups having the formula -NCX wherein X isselected from the group consisting of oxygen and sulfur, the improvedmethod of effecting the said reaction comprising carrying out the saidreaction in the presence of from about 0.001 percent to about 5 percentby wei ht of a catalyst selected from the group consisting of the oxidesand hydroxides of alkali and aikaline earth metals; the oxides of zincand lead; the alkali metal salts of substituted phenols; and uncomplexedquaternary ammonium compounds.

10. in a method for making nonporous polyurethane plastics by a processwhich comprises reacting an organic compound having at least two groupsselected from the group consisting of hydroxyl, carboxyl, primary amino,secondary amino and mercapto groups, said groups being the only groupsreactive with an -NCX group, with an organic compound having as its solereactive groups a plurality of separate and distinct groups having theformula --NCX wherein X is selected from the group consisting of oxygenand sulfur, the improved method of effecting the said reaction Whichcomprises bringing the said components together along with an inertorganic solvent for the resulting adduct having a boiling point belowabout 200 C. and from about 0.001 percent to about 5 percent by weightof a catalyst selected from the group consisting of the oxides andhydroxides of alkali and alkaline earth metals; the oxides of zinc andlead; the alkali metal salts of substituted phenols; and uncomplexedquaternary ammonium compounds.

11. The method of claim 8 wherein the NCX groups are NCO groups.

12. The method of claim 8 wherein the NCX groups are NCS groups.

13. In a method for making nonporous polyurethane plastics by a processwhich comprises reacting a polyoxyalkylene glycol with an organiccompound having as its sole reactive groups a plurality of separate anddistinct groups having the formula --NCX wherein X is selected from thegroup consisting of oxygen and sulfur, the improved method of effectingthe said reaction comprising carrying out the said reaction in thepresence of from about 0.001 percent to about 5 percent by weight of acatalyst selected from the group consisting of the oxides and hydroxidesof alkali and alkaline earth metals; the oxides of zinc and lead; thealkali metal salts of substituted phenols; and uncomplexed quaternaryammonium compounds.

14. A method for making a nonporous polyurethane containing biuret andallophanate groups along with urethane linkages which comprises reactinga polyether glycol, with an organic compound having as its sole reactivegroups at least two separate and distinct groups having the formula -NCXwherein X is selected from the group consisting of oxygen and sulfur inthe presence of from lll about 0.001 percent to about percent by weightof a compound which promotes formation of allophanates and biurets andis selected from the group consisting of the oxides and hydroxides ofalkali and alkaline earth metals, the oxides of zinc and lead, thealkali metal salts of substituted phenols; and uncomplexed quaternaryammonium compounds.

15. A method for making a nonporous polyurethane containing biuret andallophanate groups along with urethane linkages which comprises reactingan organic compound having at least two groups selected from the groupconsisting of hydroxyl, carboxyl, primary amino, secondary amino, andmercapto groups, with an organic compound having as its sole reactivegroups at least two separate and distinct groups having the formula NCXwherein X is selected from the group consisting of oxygen and sulfur inan inert organic solvent for the resulting reaction product, saidsolvent having a boiling point below about 200 C. and selected from thegroup consisting of hydrocarbons, chloro hydrocarbons, ketones andesters in the presence of from about 0.001 percent to about 5 percent byweight of a compound which promotes formation of allophanates andbiurets and is selected from the group consisting of the oxides andhydroxides of alkali and alkaline earth metals, the oxides of zinc andlead, the alkali metal salts of substituted phenols, and uncomplexedquaternary ammonium compounds.

16. The composition of claim 1 wherein R is hydrocarbon.

17. The composition of claim 1 wherein R is aliphatic.

18. The composition of claim 1 wherein R is aromatic.

19. The composition of claim 1 wherein n is 2-3.

20. The product of claim 3 wherein said laminae are glass.

21.. As a new composition of matter, an adhesive composition of greatlyaccelerated curing rate comprising a solution in an organic solventboiling below about 200 C. at atmospheric pressure of an organicmaterial obtained by reacting a compound of the general formula: R(NCX)wherein R is an organic radical free from functional groups other than-NCX groups, X is selected from the group consisting of oxygen andsulfur, and n is an integer having a value of at least 2, with anorganic compound having as the only groups reactive with an -NCX groupat least two groups selected from the group consisting of hydroxyl,carboxyl, primary amino, secondary amino and mercapto groups, saidsolution containing from about 0.001 percent to about 5 percent byweight of a sodium salt of a substituted phenol.

References Cited by the Examiner UNITED STATES PATENTS 2,512,671 6/1950Novotny et al. 260-328 2,730,518 1/1956 Birley et al. 260-75 2,798,8597/1957 Bruce 260-75 2,879,251 3/1959 Seegar et al. 260-75 2,948,6918/1960 Windemuth et al. 260-336 FOREIGN PATENTS 649,928 2/1951 GreatBritain.

808,285 7/ 1951 Germany.

509,608 3/ 1952 Belgium.

OTHER REFERENCES De Bell, German Plastics Practice, Murray Printing Co.,1946, pp. 300-316, and 472-473.

MORRIS LIEBMAN, Primary Examiner.

DANIEL ARNOLD, ALEXANDER H. BRODMERKEL,

Examiners.

1. AS A NEW COMPOSITION OF MATTER, AN ADHESIVE COMPOSITION OF GREATLYACCELERATED CURING RATE COMPRISING A SOLUTION IN AN ORGANIC SOLVENTBOILING BELOW ABOUT 200*C. AT ATMOSPHERIC PRESSURE OF AN ORGANICMATERIAL OBTAINED BY REACTING A COMPOUND OF THE GENERAL FORMULA: R(NCX)NWHEREIN R IS AN ORGANIC RADICAL FREE FROM FUNCTIONAL GROUPS OTHER THAN-NCX GROUPS, X IS SELECTED FROM THE GROUP CONSISTING OF OXYGEN ANDSULFUR, AND N IS AN INTEGER HAVING A VALUE OF AT LEAST 2, WITH ANORGANIC COMPOUND HAVING AS THE ONLY GROUPS REACTIVE WITH AN -NCX GROUPAT LEAST TWO GROUPS SELECTED FROM THE GROUP CONSISTING OF HYDROXYL,CARBOXYL, PRMARY AMINO, SECONDARY AMINO AND MERCAPTO GROUPS, SAIDSOLUTION CONTAINING FROM ABOUT 0.001 PERCENT TO ABOUT 5 PERCENT BYWEIGHT OF A CATALYST SELECTED FROM THE GROUP CONSISTING OF THE OIDES ANDHYDROXIDES OF ALKALI AND ALKALINE EARTH METALS; THE OXIDES OF ZINC ANDLEAD; THE ALKALI METAL SALTS OF SUBSTITUTED PHENOLS; AND THE UNCOMPLEXEDQUATERNARY AMMONIUM COMPOUNDS.